CN115626962B - Emulsion type thickening agent and preparation method and application thereof - Google Patents
Emulsion type thickening agent and preparation method and application thereof Download PDFInfo
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- CN115626962B CN115626962B CN202211348673.7A CN202211348673A CN115626962B CN 115626962 B CN115626962 B CN 115626962B CN 202211348673 A CN202211348673 A CN 202211348673A CN 115626962 B CN115626962 B CN 115626962B
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- 239000002562 thickening agent Substances 0.000 title claims abstract description 69
- 239000000839 emulsion Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 32
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 31
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 28
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims abstract description 26
- 229940001584 sodium metabisulfite Drugs 0.000 claims abstract description 26
- 235000010262 sodium metabisulphite Nutrition 0.000 claims abstract description 26
- MJIBIURSZLQJSI-UHFFFAOYSA-N CCCCCCC=C.c1ccccc1 Chemical compound CCCCCCC=C.c1ccccc1 MJIBIURSZLQJSI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 230000001105 regulatory effect Effects 0.000 claims abstract description 15
- 230000009471 action Effects 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 abstract description 11
- 239000003431 cross linking reagent Substances 0.000 abstract description 8
- 238000010276 construction Methods 0.000 abstract description 7
- 125000003172 aldehyde group Chemical group 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 5
- 238000002347 injection Methods 0.000 abstract description 4
- 239000007924 injection Substances 0.000 abstract description 4
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 230000001965 increasing effect Effects 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 72
- 239000000203 mixture Substances 0.000 description 12
- 239000007800 oxidant agent Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004908 Emulsion polymer Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/14—Peroxides
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/725—Compositions containing polymers
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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Abstract
The invention discloses an emulsion type thickening agent and a preparation method and application thereof, wherein the preparation method comprises the steps of dissolving 3, 5-tetrabromomethyl benzene octene and butyl acrylate into white oil under the action of OP-10 and sodium dodecyl sulfate to obtain an oil phase; fully stirring and uniformly mixing acrylamide and water, and adding tert-butyl hydroperoxide to obtain a water phase; mixing the oil phase and the water phase, regulating the pH value of the system, adding sodium metabisulfite, keeping the room temperature for reaction, and then heating and continuing the reaction to obtain the emulsion type thickener for acidizing and fracturing. The emulsion thickener has strong sensitivity to acidic conditions, dihalogenated groups in the molecules of the emulsion thickener can generate aldehyde groups for crosslinking under the acidic conditions, the viscosity of the system is increased, the emulsion thickener can be crosslinked automatically under the well, the effect of the crosslinking agent is effectively achieved, other crosslinking agents are avoided being additionally added, the viscosity of the system is low during injection, construction is facilitated, and the construction period is effectively shortened.
Description
Technical Field
The invention belongs to the technical field of preparation of functional thickening agents, and relates to an emulsion type thickening agent, a preparation method and application thereof.
Background
In the exploitation process of oil fields, especially the exploitation process of low permeability oil, because the geology of low permeability oil is compact and complicated, the development difficulty is also great, and in order to remove the organic and inorganic plugs formed in the stratum, the exploitation efficiency of the low permeability old well is improved, and the acidizing fracturing technology is an effective measure which can be generally selected at present, and becomes an important measure for increasing the yield of the oil and gas well. In acidizing fracturing processes, the role of the viscosifier is important, and the proppant may be carried into the formation after the cross-linking of the cross-linking agent. At present, the conventional fracturing thickening agent is mainly prepared by polymerizing acrylamide and other monomer substances. However, the thickener needs to be added with a cross-linking agent during injection, so that the viscosity after liquid preparation is high and the construction period is long.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an emulsion type thickener, and a preparation method and application thereof, thereby effectively solving the technical problems of large viscosity and long construction period after liquid preparation caused by adding a cross-linking agent in the use process of the existing thickener.
The invention is realized by the following technical scheme:
an emulsion thickener comprising the general formula:
wherein, the value range of a is 50-100, the value range of b is 500-2500, and the value range of c is 50-100.
The emulsion thickener is applied to oilfield acidizing and fracturing.
The preparation method of the emulsion thickener comprises the following steps:
3, 5-tetrabromomethyl benzene octene and butyl acrylate are dissolved in white oil under the action of OP-10 and sodium dodecyl sulfate to obtain an oil phase;
fully stirring and uniformly mixing acrylamide and water, and adding tert-butyl hydroperoxide to obtain a water phase;
mixing the oil phase with the water phase, regulating the pH value of the system, adding sodium metabisulfite, keeping the room temperature for reaction, and then heating and continuing the reaction to obtain the emulsion type thickener for acidizing and fracturing.
Preferably, after the oil phase and the water phase are mixed, the pH value of the system is regulated to 6-8.
Preferably, after sodium metabisulfite is added, the temperature is raised to 60-70 ℃ after the reaction at room temperature, and the reaction is continued for 6-8 hours.
Preferably, the mass ratio of the 3, 5-tetrabromomethyl benzene octene to the butyl acrylate is 1 (0.3-0.5).
Preferably, the sum of the masses of the OP-10 and the sodium dodecyl sulfate is 1 to 1.5 percent of the total mass of the 3, 5-tetrabromomethylbenzene octene, the butyl acrylate and the white oil.
Preferably, the mass ratio of the acrylamide to the water is 1 (15-20); the mass of the tert-butyl hydroperoxide is 0.5-1% of the total mass of the acrylamide and the water.
Preferably, the mass ratio of the oil phase to the water phase is 1 (2-3).
Preferably, the mass of the sodium metabisulfite is 1-2% of the total mass of the water phase.
Compared with the prior art, the invention has the following beneficial technical effects:
the emulsion thickener has strong sensitivity to acidic conditions, dihalogenated groups in molecules of the emulsion thickener can generate aldehyde groups to crosslink under the acidic conditions, so that the viscosity of the system is increased, the emulsion thickener can crosslink automatically under the well, the effect of the cross-linking agent is effectively achieved, other cross-linking agents are avoided being additionally added, the viscosity of the system is low during injection of the thickener, construction is facilitated, and the construction period is effectively shortened.
The preparation method of the emulsion type thickening agent adopts OP-10 and sodium dodecyl sulfate as emulsifying agents for compounding, and meets the emulsification process of raw materials of 3, 5-tetrabromomethyl benzene octene and butyl acrylate. Meanwhile, tert-butyl hydroperoxide is adopted as an oxidant, and the oxidant has good thermal stability and is easy to control the reaction process. Meanwhile, sodium metabisulfite is used as a reducing agent, so that the reducing property is strong, and the reaction is facilitated. The preparation process has reasonable design and convenient operation, and is easy for industrialized mass production.
Further, after the oil phase and the water phase are mixed, the pH value of the system is adjusted to 6-8, and because the thickener to be prepared in the invention is used in acidizing and fracturing, the pH of the system is firstly adjusted to be neutral, and if the pH is too low, the dihalide bond in the prepared thickener can react in advance under the acidic condition to become aldehyde group, so that the thickener is unfavorable for underground use.
Further, after sodium metabisulfite is added, the temperature is raised to 60-70 ℃ after the reaction at room temperature, and the reaction is continued for 6-8 hours, so that the reaction is more sufficient, and the reaction yield is improved.
Further, the mass ratio of 3, 5-tetrabromomethyl benzene octene to butyl acrylate is 1 (0.3-0.5), and the reaction can be more sufficient within the range of the ratio, so that the yield is improved.
Furthermore, the sum of the masses of OP-10 and sodium dodecyl sulfate is 1 to 1.5 percent of the total mass of 3, 5-tetrabromomethyl benzene octene, butyl acrylate and white oil, so that the effect of the emulsifier of the system can be best.
Further, the mass of the tert-butyl hydroperoxide is 0.5% -1% of the total mass of the acrylamide and the water, and the reaction can be more sufficient within the proportion range, so that the yield is improved.
Furthermore, the mass ratio of the oil phase to the water phase is 1 (2-3), the reaction can be more sufficient within the range of the ratio, the yield is improved, and the thickening effect of the system is the best.
Furthermore, the mass of the sodium metabisulfite is 1-2% of the total mass of the water phase, so that the reaction is more complete, and the yield is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a block diagram of an emulsion thickener for acidizing fracturing of the present invention;
FIG. 2 is a schematic illustration of the preparation of an emulsion thickener for acidizing fracturing in accordance with the present invention;
FIG. 3 is a schematic cross-linking diagram of the emulsion thickener for acidizing and fracturing of the present invention under acidic conditions;
FIG. 4 is a FTIR chart of an emulsion thickener for acidizing fracturing of the present invention;
FIG. 5 shows the viscosity of the emulsion thickener for acidizing fracturing prepared in example 3 according to the present invention with pH.
Detailed Description
So that those skilled in the art can appreciate the features and effects of the present invention, a general description and definition of the terms and expressions set forth in the specification and claims follows. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and in the event of a conflict, the present specification shall control.
The theory or mechanism described and disclosed herein, whether right or wrong, is not meant to limit the scope of the invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features such as values, amounts, and concentrations that are defined herein in the numerical or percent ranges are for brevity and convenience only. Accordingly, the description of a numerical range or percentage range should be considered to cover and specifically disclose all possible sub-ranges and individual values (including integers and fractions) within the range.
Herein, unless otherwise indicated, "comprising," "including," "having," or similar terms encompass the meanings of "consisting of … …" and "consisting essentially of … …," e.g., "a includes a" encompasses the meanings of "a includes a and the other and" a includes a only.
In this context, not all possible combinations of the individual technical features in the individual embodiments or examples are described in order to simplify the description. Accordingly, as long as there is no contradiction between the combinations of these technical features, any combination of the technical features in the respective embodiments or examples is possible, and all possible combinations should be considered as being within the scope of the present specification.
The invention provides an emulsion type thickener for acidizing and fracturing, which is preferably used in oilfield acidizing and fracturing, and has the following structural formula as shown in figure 1:
wherein a, b and c are polymerization degree, the value range of a is 50-100, the value range of b is 500-2500, and the value range of c is 50-100.
As shown in fig. 2, the preparation process is realized by the following reactions:
the specific preparation process comprises the following steps:
(1) 3, 5-tetrabromomethyl benzene octene and butyl acrylate are dissolved in white oil under the action of OP-10 (dodecylphenol polyoxyethylene ether) and sodium dodecyl sulfate to obtain an oil phase;
wherein the mass ratio of 3, 5-tetrabromomethyl benzene octene to butyl acrylate to white oil is 1 (0.3-0.5) 15; the mass ratio of OP-10 to sodium dodecyl sulfate is (1-1.2), and the sum of the mass of 3, OP-10 and sodium dodecyl sulfate is 1-1.5% of the total mass of 3, 5-tetrabromomethyl benzene octene, butyl acrylate and white oil.
(2) Fully and uniformly stirring acrylamide and water at 60 ℃, and adding tert-butyl hydroperoxide as an oxidant to obtain a water phase;
wherein the mass ratio of the acrylamide to the water is 1 (15-20), and the mass of the tert-butyl hydroperoxide is 0.5-1% of the total mass of the acrylamide and the water.
(3) Mixing the oil phase and the water phase, regulating the pH value to be 6-8, dropwise adding sodium metabisulfite as a reducing agent, wherein the dropwise adding mode is more beneficial to controlling the reaction rate, so that the reaction is more complete, the room temperature is kept for 3 hours, then the temperature is raised to 60-70 ℃ for 6-8 hours, and the emulsion type thickening agent is obtained.
Wherein the dosage ratio of the oil phase to the water phase is 1 (2-3); the mass of the sodium metabisulfite is 1-2% of the total mass of the water phase.
The emulsion thickener can be used as a thickener for the acidizing and fracturing process of an oil field, and when the emulsion thickener is used as the thickener, the pH value of the underground environment of the oil field is 2-3.
As shown in fig. 3, the thickening principle is mainly as follows: the synthesized emulsion polymer is used as a thickener for acidizing fracturing fluid, and dihalide bonds in polymer molecules become aldehyde groups under the downhole acidic condition so as to crosslink, thereby enhancing the viscosity of the system. The reaction process of the polymer molecule acidification and crosslinking is as follows:
the invention discloses an emulsion type thickening agent for acidizing and fracturing, which is prepared from 3, 5-tetrabromomethyl benzene octene, acrylamide and butyl acrylate serving as raw materials through emulsion polymerization reaction. Because the dihalogenated group in the emulsion thickener molecule can generate aldehyde group to crosslink under the acidic condition, the emulsion thickener has the characteristics of avoiding using a crosslinking agent, has lower system viscosity during injection, and is beneficial to construction; in addition, the emulsion thickener is obtained by adopting a conventional emulsion polymerization method, has simple synthesis steps and is convenient for large-scale production; finally, the emulsion type thickener has strong sensitivity to acidic conditions, can generate crosslinking reaction under the acidic conditions, increases the viscosity of the system, and has strong pertinence to acidizing and fracturing.
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The following examples use instrumentation conventional in the art. The experimental methods, in which specific conditions are not noted in the following examples, are generally conducted under conventional conditions or under conditions recommended by the manufacturer. The following examples used various starting materials, unless otherwise indicated, were conventional commercial products, the specifications of which are conventional in the art. In the description of the present invention and the following examples, "%" means weight percent, and "parts" means parts by weight, and ratios means weight ratio, unless otherwise specified.
Example 1
(1) 6.135g of 3, 5-tetrabromomethylbenzene and 1.84g of butyl acrylate are dissolved in 92.025g of white oil under the action of 0.25g of OP-10 and 0.75g of sodium dodecyl sulfate, and the mixture is stirred uniformly to obtain an oil phase;
(2) 15.625g of acrylamide and 234.375g of water are fully and uniformly stirred at 60 ℃, 1.25g of tert-butyl hydroperoxide is added, and the mixture is uniformly stirred to obtain a water phase;
(3) Mixing 66.667g of the oil phase and 133.333g of the water phase, regulating the pH value to be 6, dropwise adding 1.333g of sodium metabisulfite, keeping the room temperature for reaction for 3 hours, and then raising the temperature to 60 ℃ for reaction for 6 hours to obtain the emulsion type thickening agent for acidizing and fracturing.
Example 2
(1) 4.041g of 3, 5-tetrabromomethylbenzene and 2.02g of butyl acrylate are dissolved in 60.609g of white oil under the action of 0.285g of OP-10 and 0.715g of sodium dodecyl sulfate, and the mixture is stirred uniformly to obtain an oil phase;
(2) 11.905g of acrylamide and 238.095g of water are fully and uniformly stirred at 60 ℃, 2.5g of tert-butyl hydroperoxide is added, and the mixture is uniformly stirred to obtain a water phase;
(3) Mixing 50g of the oil phase and 150g of the water phase, regulating the pH value to 7, dropwise adding 3g of sodium metabisulfite, keeping the room temperature for reaction for 3 hours, and then raising the temperature to 70 ℃ for reaction for 7 hours to obtain the emulsion type thickening agent for acidizing and fracturing.
Example 3
(1) 6.098g of 3, 5-tetrabromomethylbenzene and 2.44g of butyl acrylate are dissolved in 94.462g of white oil under the action of 0.25g of OP-10 and 0.75g of sodium dodecyl sulfate, and the mixture is stirred uniformly to obtain an oil phase;
(2) 13.89g of acrylamide and 236.11g of water are fully and uniformly stirred at 60 ℃, 2g of tert-butyl hydroperoxide is added, and the mixture is uniformly stirred to obtain a water phase;
(3) Mixing 50g of the oil phase and 150g of the water phase, regulating the pH value to 7, dropwise adding 2.25g of sodium metabisulfite, keeping the room temperature for reaction for 3 hours, and then raising the temperature to 65 ℃ for reaction for 7 hours to obtain the emulsion type thickening agent for acidizing and fracturing.
To characterize the structure of the synthesized emulsion type thickener, the emulsion type thickener prepared in this example was subjected to infrared test, and the results are shown in fig. 4. As can be seen from FIG. 4, at 3369cm -1 The position of the N-H bond has a telescopic vibration absorption peak of 2927cm -1 The position of the elastic vibration absorption peak of saturated C-H bond is at 1722cm -1 The position of the C=O bond appears in the telescopic vibration absorption peak, at 1650cm -1 And 1571cm -1 The position of the vibration absorbing peak appears in the carbon skeleton of benzene ring, at 1381cm -1 The bending vibration absorption peak of C-H bond appears at 1182cm -1 The telescopic vibration absorption peak of the C-Br bond appears at the position, which shows that the thickener molecule is successfully synthesized.
To characterize the performance of the synthesized emulsion type thickener for acid fracturing, the viscosity of the emulsion type thickener prepared in this example was tested at different pH values, and the results are shown in FIG. 5. As can be seen from fig. 5, the viscosity of the synthesized emulsion-type thickener gradually increases with the decrease of the pH, and the viscosity starts to increase dramatically at a pH of about 5, because the aldehyde groups between the molecular chains crosslink, so that the viscosity of the system increases, and the viscosity change remains stable at a pH of about 2 to 3, indicating that the emulsion-type thickener for acidizing and fracturing has higher sensitivity to acidic conditions, and can be applied to environments with a pH of about 2 to 3.
Example 4
(1) 6.135g of 3, 5-tetrabromomethylbenzene and 1.84g of butyl acrylate are dissolved in 92.025g of white oil under the action of 0.25g of OP-10 and 0.75g of sodium dodecyl sulfate, and the mixture is stirred uniformly to obtain an oil phase;
(2) 13.89g of acrylamide and 236.11g of water are fully and uniformly stirred at 60 ℃, 2g of tert-butyl hydroperoxide is added, and the mixture is uniformly stirred to obtain a water phase;
(3) Mixing 66.667g of the oil phase and 133.333g of the water phase, regulating the pH value to be 6, dropwise adding 2.667g of sodium metabisulfite, keeping the room temperature for reaction for 3 hours, and then raising the temperature to 70 ℃ for reaction for 7 hours to obtain the emulsion-type thickening agent for acidizing and fracturing.
Example 5
(1) 4.041g of 3, 5-tetrabromomethylbenzene and 2.02g of butyl acrylate are dissolved in 60.609g of white oil under the action of 0.285g of OP-10 and 0.715g of sodium dodecyl sulfate, and the mixture is stirred uniformly to obtain an oil phase;
(2) 15.625g of acrylamide and 234.375g of water are fully and uniformly stirred at 60 ℃, 1.25g of tert-butyl hydroperoxide is added, and the mixture is uniformly stirred to obtain a water phase;
(3) Mixing 57.143g of the oil phase and 142.857g of the water phase, regulating the pH value to 8, dropwise adding 2.857g of sodium metabisulfite, keeping the room temperature for reaction for 3 hours, and then raising the temperature to 70 ℃ for reaction for 8 hours to obtain the emulsion type thickening agent for acidizing and fracturing.
Example 6
(1) 6.098g of 3, 5-tetrabromomethylbenzene and 2.44g of butyl acrylate are dissolved in 94.462g of white oil under the action of 0.25g of OP-10 and 0.75g of sodium dodecyl sulfate, and the mixture is stirred uniformly to obtain an oil phase;
(2) 11.905g of acrylamide and 238.095g of water are fully and uniformly stirred at 60 ℃, 2.5g of tert-butyl hydroperoxide is added, and the mixture is uniformly stirred to obtain a water phase;
(3) Mixing 66.667g of the oil phase and 133.333g of the water phase, regulating the pH value to 7, dropwise adding 1.999g of sodium metabisulfite, keeping the room temperature for reaction for 3 hours, and then raising the temperature to 65 ℃ for reaction for 7 hours to obtain the emulsion-type thickening agent for acidizing and fracturing.
Example 7
(1) 3, 5-tetrabromomethyl benzene octene and butyl acrylate are dissolved in white oil under the action of OP-10 and sodium dodecyl sulfate to obtain an oil phase; wherein the mass ratio of the 3, 5-tetrabromomethyl benzene octene to the butyl acrylate to the white oil is 1:0.3:15; the mass ratio of OP-10 to sodium dodecyl sulfate is 1:3, and the sum of the mass ratio of OP-10 to sodium dodecyl sulfate is 1% of the total mass of 3, 5-tetrabromomethyl benzene octene, butyl acrylate and white oil.
(2) Fully and uniformly stirring acrylamide and water at 60 ℃, and adding tert-butyl hydroperoxide as an oxidant to obtain a water phase; wherein the mass ratio of the acrylamide to the water is 1:15, and the mass of the tert-butyl hydroperoxide is 0.5 percent of the total mass of the acrylamide and the water.
(3) Mixing the oil phase and the water phase, regulating the pH value to be 6, dropwise adding sodium metabisulfite as a reducing agent, keeping the room temperature for reaction for 3 hours, and then raising the temperature to 60 ℃ for reaction for 6 hours to obtain the emulsion type thickening agent. Wherein the dosage ratio of the oil phase to the water phase is 1:2; the mass of the sodium metabisulfite is 1 percent of the total mass of the water phase.
Example 8
(1) 3, 5-tetrabromomethyl benzene octene and butyl acrylate are dissolved in white oil under the action of OP-10 and sodium dodecyl sulfate to obtain an oil phase; wherein the mass ratio of the 3, 5-tetrabromomethyl benzene octene to the butyl acrylate to the white oil is 1:0.34:15; the mass ratio of OP-10 to sodium dodecyl sulfate is 1.1:3, and the sum of the mass of OP-10 and sodium dodecyl sulfate is 1.3 percent of the total mass of 3, 5-tetrabromomethyl benzene octene, butyl acrylate and white oil.
(2) Fully and uniformly stirring acrylamide and water at 60 ℃, and adding tert-butyl hydroperoxide as an oxidant to obtain a water phase; wherein the mass ratio of the acrylamide to the water is 1:17, and the mass of the tert-butyl hydroperoxide is 0.6 percent of the total mass of the acrylamide and the water.
(3) Mixing the oil phase and the water phase, regulating the pH value to 7, dropwise adding sodium metabisulfite as a reducing agent, keeping the room temperature for reaction for 3 hours, and then raising the temperature to 63 ℃ for reaction for 6.6 hours to obtain the emulsion type thickening agent. Wherein the dosage ratio of the oil phase to the water phase is 1:2.5; the mass of the sodium metabisulfite is 1.4 percent of the total mass of the water phase.
Example 9
(1) 3, 5-tetrabromomethyl benzene octene and butyl acrylate are dissolved in white oil under the action of OP-10 and sodium dodecyl sulfate to obtain an oil phase; wherein the mass ratio of the 3, 5-tetrabromomethyl benzene octene to the butyl acrylate to the white oil is 1:0.45:15; the mass ratio of OP-10 to sodium dodecyl sulfate is 1.2:3, and the sum of the mass of OP-10 and sodium dodecyl sulfate is 1.4 percent of the total mass of 3, 5-tetrabromomethyl benzene octene, butyl acrylate and white oil.
(2) Fully and uniformly stirring acrylamide and water at 60 ℃, and adding tert-butyl hydroperoxide as an oxidant to obtain a water phase; wherein the mass ratio of the acrylamide to the water is 1:18, and the mass of the tert-butyl hydroperoxide is 0.8 percent of the total mass of the acrylamide and the water.
(3) Mixing the oil phase and the water phase, regulating the pH value to 7, dropwise adding sodium metabisulfite as a reducing agent, keeping the room temperature for reaction for 3 hours, and then raising the temperature to 67 ℃ for reaction for 7 hours to obtain the emulsion type thickening agent. Wherein the dosage ratio of the oil phase to the water phase is 1:2.7; the mass of the sodium metabisulfite is 1.7 percent of the total mass of the water phase.
Example 10
(1) 3, 5-tetrabromomethyl benzene octene and butyl acrylate are dissolved in white oil under the action of OP-10 and sodium dodecyl sulfate to obtain an oil phase; wherein the mass ratio of the 3, 5-tetrabromomethyl benzene octene to the butyl acrylate to the white oil is 1:0.5:15; the mass ratio of OP-10 to sodium dodecyl sulfate is 1.2:3, and the sum of the mass of OP-10 and sodium dodecyl sulfate is 1.5 percent of the total mass of 3, 5-tetrabromomethyl benzene octene, butyl acrylate and white oil.
(2) Fully and uniformly stirring acrylamide and water at 60 ℃, and adding tert-butyl hydroperoxide as an oxidant to obtain a water phase; wherein the mass ratio of the acrylamide to the water is 1:20, and the mass of the tert-butyl hydroperoxide is 1% of the total mass of the acrylamide and the water.
(3) Mixing the oil phase and the water phase, regulating the pH value to 8, dropwise adding sodium metabisulfite as a reducing agent, keeping the room temperature for reaction for 3 hours, and then raising the temperature to 70 ℃ for reaction for 8 hours to obtain the emulsion type thickening agent. Wherein the dosage ratio of the oil phase to the water phase is 1:3; the mass of sodium metabisulfite is 2% of the total mass of the aqueous phase.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (9)
1. An emulsion thickener characterized by comprising the following general formula:
wherein, the value range of a is 50-100, the value range of b is 500-2500, and the value range of c is 50-100.
2. Use of the emulsion thickener of claim 1 in oilfield acidizing fracturing.
3. The method for preparing the emulsion thickener as claimed in claim 1, comprising the following steps:
3, 5-tetrabromomethyl benzene octene and butyl acrylate are dissolved in white oil under the action of OP-10 and sodium dodecyl sulfate to obtain an oil phase;
fully stirring and uniformly mixing acrylamide and water, and adding tert-butyl hydroperoxide to obtain a water phase;
mixing the oil phase with the water phase, regulating the pH value of the system, adding sodium metabisulfite, keeping the room temperature for reaction, and then heating and continuing the reaction to obtain the emulsion type thickening agent for acidizing and fracturing;
and adjusting the pH value of the system to 6-8.
4. The method for preparing an emulsion thickener according to claim 3, wherein after sodium metabisulfite is added, the temperature is raised to 60-70 ℃ after the reaction at room temperature, and the reaction is continued for 6-8 hours.
5. The method for preparing an emulsion thickener according to claim 3, wherein the mass ratio of 3, 5-tetrabromomethylbenzene to butyl acrylate is 1 (0.3-0.5).
6. The method for preparing an emulsion thickener according to claim 3, wherein the sum of the masses of OP-10 and sodium dodecyl sulfate is 1% -1.5% of the total mass of 3, 5-tetrabromomethyl benzene octene, butyl acrylate and white oil.
7. The method for preparing the emulsion thickener according to claim 3, wherein the mass ratio of the acrylamide to the water is 1 (15-20); the mass of the tert-butyl hydroperoxide is 0.5% -1% of the total mass of the acrylamide and the water.
8. The method for preparing an emulsion thickener according to claim 3, wherein the mass ratio of the oil phase to the water phase is 1 (2-3).
9. The method for preparing the emulsion thickener according to claim 3, wherein the mass of the sodium metabisulfite is 1% -2% of the total mass of the water phase.
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